Supercritical fluid recovery and refining of hydrocarbons from hydrocarbon-bearing formations applying fuel cell gas in situ

ABSTRACT

A plume of combined gases are infused into hydrocarbon-bearing formations, “inert” as the major gas and “reactive” as the minor gas, where the minor gas reacts with hydrocarbons to fully saturate hydrocarbons with supercritical fluid, which migrate hydrocarbons out of formations, even at great distances from the regulated fuel cell source. Coal, tar sands, petroleum-contaminated soil, and/or oil wells that have lost gas pressure can also be desorbed by this in-situ method.

TECHNICAL FIELD

The present invention is generally directed to applying a combination ofgases and waste steam produced from fuel cells to increase production inoil and natural gas fields by infusion of stable nitrogen diamers (N₂)combined with traces of hydrocarbon-reactive nitrogen compounds intohydrocarbon-bearing formations, which violently react (micro-bursts ofenergy) with hydrocarbons, compressing nitrogen into supercritical fluid(SCF) cells with orders of magnitude more penetration into hydrocarbonsthan would naturally form from nitrogen diamers migration alone. A plumeof combined gases are infused into hydrocarbon-bearing formations,“inert” as the major gas and “reactive” as the minor gas. The minor gasreacts with hydrocarbons to fully saturate hydrocarbons with SCF thatmigrates hydrocarbons out of formations, even at great distances fromthe regulated fuel cell source. When potential supercritical gases andfluids are already naturally in situ within the formation, only ahydrocarbon-reactive compound needs to be infused into the hydrocarbonformation.

BACKGROUND OF THE INVENTION

Any natural geologic hydrocarbon formations that have porosity andpermeability that allow hydrocarbons to migrate are target locations forthis invention. A fuel cell technology is applied to electrochemicallyseparate nitrogen from air and then pressurize nitrogen diamers andnitrogen compounds through hydrocarbon formations. Where nitrogencompounds violently react with hydrocarbons, a large number of SCFnucleation sites are formed from the instant compression of nitrogendiamers (N₂) into supercritical nitrogen (scN₂).

SCF cells form when hydrocarbon-reactants violently react (micro-burstsof energy) with hydrocarbons, because gas molecules travel only shortdistances in straight lines before they are deflected in a new directionby collision with other gas molecules that are further confined insidethe small pores (in geology a small space that is surrounded by rock orsoil and filled with hydrocarbon gases, fluids and solids) of naturalhydrocarbon formation rock and soil that includes fluid and solid fills.The gas velocity formula below can be applied under thekinetic-molecular theory of gases to explain why open gas permeableformations that have very small or low porosity can still have gas andliquids phase into instances of SCF cells. Prior SCF art does not teachthat open porous geologic formations can provide the environment for aSCF event to move hydrocarbons out of the formation. SCF oil and gasrecovery focuses on breaking down the hydrocarbons for movement, byminimizing or limiting chemical reactions to SCF formation.

The kinetic-molecular theory (KMT) of gases can be stated as fourpostulates:

1. A gas consists of molecules in constant random motion.

2. Gas molecules influence each other only by collision; they exert noother forces on each other.

3. All collisions between gas molecules are perfectly elastic; allkinetic energy is conserved.

4. The volume actually occupied by the molecules of a gas is negligiblysmall; the vast majority of the volume of the gas is empty space throughwhich the gas molecules are moving.

Gas Velocity Explained

The root mean square velocity of a molecule can be obtained by using theformulavrms=(3RT/M)^(1/2)

Example: Calculate the root-mean-square velocity of oxygen molecules atroom temperature, 25° C. M is the molecular mass of oxygen which is31.9998 g/mol; the molar gas constant is 8.314 J/mol K, and thetemperature is 298.15 K. The molecular mass must be divided by 1000 toconvert it into a usable form, thereforevrms=(3(8.314)(298.15)/(0.0319998))^(1/2)=481.2 m/s

So an oxygen molecule travels through the air at 481.2 m/s which is 1726km/h, much faster than a jetliner can fly and faster than that of mostrifle bullets.

The very high speed of gas molecules under normal room conditions wouldindicate that a gas molecule would travel across a room almostinstantly. In fact, gas molecules do not do so. If a small sample of avery odorous (and poisonous) gas, H2S is released in one corner of aroom, our noses will not detect it in another corner of the room forseveral minutes unless the air is vigorously stirred by a mechanicalfan. The slow diffusion of gas molecules which are moving very quicklyoccurs because the gas molecules travel only short distances in straightlines before they are deflected in a new direction by collision withother gas molecules.

The distance any single molecule travels between collisions will varyfrom very short to very long distances, but the average distance that amolecule travels between collisions in a gas can be calculated. Thisdistance is called the mean free path of the gas molecules. If theroot-mean-square velocity is divided by the mean free path of the gasmolecules, the result will be the number of collisions one moleculeundergoes per second. This number is called the collision frequency ofthe gas molecules.

The postulates of the KMT of gases permit the calculation of the meanfree path of gas molecules. The gas molecules are visualized as smallhard spheres. Without going into the mathematical detail; as thetemperature raises the mean free path increases; it also rises as thepressure decreases, and as the size of the molecules decrease. Takingall this into account, the oxygen molecules from above has a mean freepath of 67 nm. Diffusion takes place slowly because even thoughmolecules are moving very fast, they travel only short distances in anyone straight line.

This invention teaches that a propellant is a material used to move anobject by applying a motive force provided after a SCF penetration intohydrocarbons. This may or may not involve a chemical reaction. It may bea gas, liquid, plasma, or, before the chemical reaction, a solid. Assome gas escapes to expel the hydrocarbons in a formation, more new SCFforms back pressure as liquid evaporates into new gas, maintaining amotive force of pressure. Pressure acts in all directions at a pointinside a gas. At the surface of a gas, the pressure force actsperpendicular to the surface forcing gases, liquids, and solids out ofthe formation.

This invention teaches spontaneous reactions (in opposition tonon-spontaneous reactions) do not need external perturbations (such asenergy supplement at the oil well borehole) to happen at a greatdistance from the infusion of reactants at borehole. An irreversiblereaction is one in which nearly all of the reactants (minor gas) areused to form products. These reactions are very difficult to reverseeven under extreme conditions. Although all reactions are reversible tosome extent, this invention focuses on reactions that can be classifiedas irreversible. A reaction is called spontaneous if itthermodynamically causes a net increase on global entropy. In ahydrocarbon bearing formation at chemical equilibrium, it is expected tohave larger concentrations of the substances formed from SCF formingback pressure as liquid evaporates into new gas in the spontaneousdirection of the reaction, maintaining a motive force of pressure awayfrom the reactant source borehole. Every chemical reaction is, intheory, reversible. In a forward reaction the substances defined asreactants are converted to products. In a reverse reaction products areconverted into reactants. Chemical equilibrium is the state in which theforward and reverse reaction rates are equal, thus preserving the amountof reactants and products. A reaction in equilibrium can be driven inthe forward or reverse direction by changing reaction conditions such astemperature or pressure elevated by SCF formation. Le Chatelier'sprinciple can be used to predict whether products or reactants will beformed from reactions that form SCFs.

Le Chatelier's Principle can be summarized: When a chemical system atequilibrium experiences a change in concentration, temperature or totalpressure the equilibrium will shift in order to minimize that change.The principle is used by chemists in order to manipulate the outcomes ofreversible reactions, often to increase the yield of reactions.

Concentration of an ingredient will shift the equilibrium to the sidethat would reduce that change in concentration. This can be illustratedby the equilibrium of carbon monoxide and hydrogen gas, reacting to formmethanol.CO+2H2

CH3OH

Suppose we were to increase the concentration of CO in the system. UsingLe Chatelier's principle we can predict that the amount of methanol willincrease, decreasing the total change in CO.

Temperature: Let us take for example the reaction of nitrogen gas withhydrogen gas. This is a reversible reaction, in which the two gasesreact to form ammonia:N2+3H2

2NH3ΔH=−92 kJ/mol

This is an exothermic reaction when producing ammonia. If we were tolower the temperature, the equilibrium would shift in such a way as toproduce heat. Since this reaction is exothermic to the right, it wouldfavour the production of more ammonia. This reaction is used in theHaber process, which is a good example of the way chemists use LeChatelier's principle.

In a Total Pressure manipulation we can refer to the reaction ofnitrogen gas with hydrogen gas to form ammonia:N2+3H2

2NH3ΔH=−92 kJ/mol

Note the number of moles of gas on the left hand side, and the number ofmoles of gas on the RHS. We know that gases at the same temperature andpressure will occupy the same volume. We can use this fact to predictthe change in equilibrium that will occur if we were to change the totalpressure.

Suppose we increase total pressure on the system, now by Le Chatelier'sprinciple the equilibrium would move to decrease the pressure. Notingthat 4 moles of gas occupy more volume than 2 moles of gas, we candeduce that the reaction will move to the right if we were to increasethe pressure.

Nitrous oxide (N₂O), ammonia (NH₃), and hydrazine (N₂H₄) are nitrogencompounds that are target gas and violently react with hydrocarbons.Nitrous oxide or ammonia or hydrazine or nitric acid (HNO₃) compoundswill react with hydrocarbons. Ammonia and hydrazine react explosivelywith petroleum.

Nitrogen tetroxide (or dinitrogen tetroxide) (N₂O₄) is a hypergolicpropellant often used in combination with a hydrazine-based rocket fuel.The combination was used to fuel the Titan rockets used in the Geminimissions, and it is still used today in the second stage engines ofDelta II rockets. By the late 1950s, it became the storable oxidizer ofchoice for rockets in both the USA and USSR.

Nitrogen dioxide is made by the catalytic oxidation of ammonia: steam isused as a diluent to reduce the combustion temperature. Most of thewater is condensed out, and the gases are further cooled; the nitricoxide that was produced is oxidized to nitrogen dioxide, and theremainder of the water is removed as nitric acid. The gas is essentiallypure nitrogen tetroxide, which is condensed in a brine-cooled liquefier.

Nitrogen tetroxide is a liquid that is easily vaporized. It is apowerful oxidizer and is highly toxic and corrosive. It is not affectedby mechanical shock and does not react with air. Nitrogen tetroxide isalways in equilibrium with nitrogen dioxide (NO₂), and some nitrogendioxide will be present in any quantity of nitrogen tetroxide (highertemperatures push the equilibrium towards nitrogen dioxide). Nitrogentetroxide reacts with water to form nitric acid.

Reactions of Nitric Acid

Dinitrogen pentoxide, N₂O₅, is best prepared by dehydrating concentratednitric acid, HNO₃, by phosphorus pentoxide, P₂O₅.2HNO₃+P₂O₅

N₂O₅+2HPO₃

Nitric oxide, NO, is prepared by the action of copper, Cu, or mercury,Hg, on dilute nitric acid, HNO₃, and was called nitrous air.3Cu+8HNO₃

3Cu(NO₃)2+2NO+4H₂O

Nitrogen dioxide, NO₂, is a mixed acid anhydride and reacts with waterto give a mixture of nitrous and nitric acids.2NO₂+H₂

HNO₂+HNO₃

If the solution is heated, the nitrous acid decomposes to give nitricacid and nitric oxide.3HNO₂

HNO₃+2NO+H₂O

Sulphur dioxide, SO₂, and nitrogen oxides, NO_(x), are toxic acidicgases, which readily react with the water in the atmosphere to form amixture of sulphuric acid, nitric acid, and nitrous acid as acid rain.

Nitrates are the salts of nitric acid and are strong oxidizing agents.

The Oswald Process is the three-stage process by which nitric acid ismanufactured. First, ammonia, NH₃, is oxidized at a high temperature(900° C.) over a platinum-rhodium catalyst to form nitrogen monoxide,NO.4NH₃ (g)+5O₂ (g)

4NO (g)+6H₂O

The nitrogen monoxide, NO, cools and reacts with oxygen, O₂, to producenitrogen dioxide, NO₂.2NO (g)+O₂

2NO₂ (g)

Finally, the nitrogen dioxide, NO₂, reacts with water and oxygen, O₂, toproduce nitric acid,4NO₂ (g)+2H₂O (l)+O₂

4HNO₃ (l)

All oxides of nitrogen are polar covalent compounds. The lower oxides ofnitrogen are neutral oxides. The higher oxides of nitrogen are acidicoxides. The oxides of nitrogen are formed during high temperaturecombustion, and are present in exhaust gases from these processes. Theprincipal oxides of nitrogen, NO_(x), are nitrous oxide, nitric oxide,nitrogen dioxide, nitrogen pentoxide, and dinitrogen tetroxide.Combustion emissions are typically optimized to reduce NO_(x). Thisinvention teaches that high temperature combustion processes can bemodified to produce higher volumes of oxides of nitrogen that arereactive with hydrocarbon, under pressure of exhaust, and can be infusedinto hydrocarbon formations to form SCF and propulsion of hydrocarbonsout of the formation. A combustion engine, fuel cell, or turbine can bemodified to optimize the production of combustion NO_(x) emissions to avolume high enough to reinject into a geologic formation. Piston,combustion chamber, fuel to air mixtures, exhaust, intake, and pollutioncontrols can be removed to accomplish this gas supply in an engine.Turbine intake, exhaust, fuel to air mixtures, turbine speed, operatingtemperatures, and pressures can be reduced in efficiency to produce highNO_(x) emission for injection into oil formations. An alternative tofuel cells, Air Liquide of Houston Tex. USA provides FLOXAL™ solutions(FLOXAL™ Nitrogen, FLOXAL™ Oxygen, FLOXAL™ Hydrogen and FLOXAL™ Air),which are adapted in real time to production volume requirements, payingattention to continuity of supply.

A general solubility property of gases (a behavior described by Graham'sLaw and by Dalton's Law of Partial Pressures) is that they diffuse tofill the volume in which they are contained. Gases have neither fixedshape nor fixed volume; therefore, gases that do not react with eachother are infinitely soluble in each other in all proportions due tothis power of diffusion. SCF form from gas species and progress tocombine with liquids that are in an SCF state, forming one solution thatpenetrates hydrocarbon solids at nearly 100 percent, moving thehydrocarbons with the greatest efficiency.

A gas that dissolves in a liquid with which it does not react isuniformly distributed throughout the volume of the solvent, and itsbehavior is described by Henry's Law. Generally, the solubility of a gasthat is only slightly soluble in a solvent decreases with increasingtemperature. Hydrogen, nitrogen and oxygen are non-polar and are onlyslightly soluble in water. In the case of these three gases, the gasescontinue to exist as covalent molecules in solution and there is nosignificant alteration to the structure of the molecules of gas.Hydrogen and nitrogen make the ideal SCFs because of this behavior.

A polar covalent gas that dissolves in a polar solvent often undergoeschemical reaction with the solvent, and significant changes to thestructure of the molecules of the gas occur in solution (e.g. the polarcovalent gas ammonia is very soluble in water and in aqueous solution,ammonia exists as an ammonium ion, NH₄(+), having extracted a hydrogenion from a molecule of water). Ammonia, NH₃+H₂

ammonium ion NH₄(+)+hydroxyl ion HO(−). The resulting solution isalkaline due to the existence of the hydroxyl ion in solution.

Hydrocarbon reactants other than nitrogen compounds are taught in thisinvention. Hydroxyl radicals act like a detergent (and can be carried insuspension as a neutral solution), reacting with carbon monoxide,methane, and other hydrocarbons and so oxidizing them to form scWaterand scCarbon dioxide miscible SCFs in situ. Hydroxyl radicals reactionsmove hydrocarbons out of formation, and are significant replacements forother gases (or liquids) when there is too much water for anhydrousammonia to adsorb. Alternative SCF reactions are important, becausenature is not the same for each geologic formation. Water alone can beremoved from the ground from the infusion of hydroxyl radicals.

Hydroxide is a polyatomic ion consisting of oxygen and hydrogen:—O—H

It has a charge of −1. Hydroxide is one of the simplest of thepolyatomic ions. The term hydroxyl group is used to describe thefunctional group —OH when it is a substituent in an organic compound.Organic molecules containing a hydroxyl group are known as alcohols (thesimplest of which have the formula CnH₂n+1-OH). A group of basescontaining hydroxide are called hydroxide bases. Hydroxide bases willdissociate into a cation and one or more hydroxide ions in water, makingthe solution basic. Hydrogen hydroxide is another name for water, as ishydrohydroxic acid. Both names are based on the hydroxide ion. Thehydroxyl radical, OH, is the neutral form of the hydroxide ion. Hydroxylradicals are highly reactive and consequently short lived. Most notably,hydroxyl radicals are produced from the decomposition of hydro-peroxides(ROOH).

This invention focuses on providing the process of SCF only whenhydrocarbons are present, which offers a wide range of solvent power ata great distance from the source, chemical selectivity, environmentalcontrol, economics, and safety. This invention uses SCFs as anenvironmentally acceptable alternative to conventional solvents forreaction chemistry in hydrocarbon oil and gas recovery.

This invention teaches environmental control and safety by selectingreaction compound species for their entropy, enthalpy, and economy involumes that react violently under the critical point in open spaces ofthe formation and above the critical point, forming SCF when the samereaction occurs in substantially higher density formations where theconcentration, temperature, and pressure can produce a motive pressure.In many cases, the porosity, or open cavity, will be so great in volumethat a SCF potential fluid will not form from a violent reaction,because the reaction zone cannot build pressure and temperature rapidlyenough to move above the critical point. The violent reaction stilldevelops pressure to move hydrocarbons out of a formation and is underthe spirit of this invention where the reaction simply becomes apropellant to move hydrocarbons. This invention teaches an SCF formsfrom violent reaction (micro-bursts of energy) with hydrocarbons withinthe confinement of high-density porous hydrocarbon formations in whichthe substance at a temperature and pressure rises instantaneously aboveits thermodynamic critical point, penetrating and moving thehydrocarbons from the solvent penetrating energy power of an SCF. Innature there is an infinitely variable set of formation sizes, depths,porosities, formation materials, hydrocarbon mixtures, and quantities ofeach.

An SCF is any substance at a temperature and pressure above itsthermodynamic critical point (FIG. 14). SCFs have the unique ability todiffuse solids, like a gas, and dissolve materials into theircomponents, like a liquid. Furthermore, SCFs can readily change indensity above the critical point and still remain in a supercriticalstate. Rapid expansion of supercritical solutions can lead toprecipitation of a finely divided solid. SCF extraction is a processwith properties that make SCFs suitable as a substitute for organicsolvents. Carbon dioxide (CO₂) and water are commonly used as SCFs forthis purpose. Supercritical scCO₂ (Tc=31.1° C., Pc=73.8 bar) closelyresembles n-hexane in its solvating power, which can be further tuned bythe addition of modifiers (including co-solvents and phase transfercatalysts) to afford the solubility characteristics required by thereaction selected for. Water's critical point occurs at around Tc=647 K(374° C. or 705° F.) and Pc=22.064 MPa (3200 PSIA), providing scH₂O. SCFis defined by the critical temperature and pressure of any substance.SCFs have solvent power similar to a light hydrocarbon for most solutes.Fluorinated compounds are often more soluble in scCO₂ than inhydrocarbons. Solubility increases with increasing density, which isprovided from increasing pressure. Fuel cells require gases that arebroken down from their original complex hydrocarbon to process thesimple gas across the fuel cell membranes, and these complexhydrocarbons are broken down in situ by SCF's migration within thehydrocarbon formation.

Fluids such as supercritical xenon, ethane, and carbon dioxide offer arange of unusual chemical possibilities in both synthetic and analyticalchemistry. Supercritical carbon dioxide is the most widely studied.Others include nitrogen, propane, propene, butane, xenon, ethane, andwater. The effect is similar to a normalizing constant. The fluids arecompletely miscible with permanent gases (e.g. N₂ or H₂), and this leadsto much higher concentrations of dissolved gases than can be achieved inconventional solvents. This effect is applied in both organometallicreactions and hydrogenation.

SCF modifier solvents: Small amounts of a second solvent can be added tothe SCF. This can result in a change in solvent polarity and nature,which follows Snyder rules. This requires a proton donor (1-2-propanol),proton acceptor (2-acetonitrile), and dipole (3-dichloromethane).Synthetic organic chemists, inorganic chemists, physical chemists, andchemical physicists who employ a synergic blend of experimental,theoretical, and computational techniques can identify target compounds,attempt their synthesis on a laboratory scale, characterize newmaterials, and perform larger-scale synthesis of promising new speciesfor formulation and application as SCFs to remove hydrocarbons fromgeologic formations. SCFs can be combined in any number of materials andcan be synthetic or natural material combinations that will penetratethe hydrocarbon-bearing formation. Natural gases and decomposedhydrocarbons from hydrocarbon-bearing formations can be phased into SCFsas part of the supercritical process of extraction.

Robert Frisbee of Jet Propulsion Laboratory (JPL) researched ways ofincorporating a little monatomic hydrogen into anything with even alittle stability for application in ultra-high performance propulsionfor planetary spacecraft. A selected list of propellants (adapted fromFrisbee, 1983) demonstrates: solids (IUS(3) â‰^3.0 m/s),monopropellants, bipropellants, and tripropellants, free radicals(unstable), and nuclear thermal (â‰^3500K). These propellants areman-made for rocket propulsion; in contrast, oil recovery is natural andwill have many more gas species grouped together in excess oftripropellants as part of SCFs and propellants. The high number ofnatural gas species in the infinitely variable hydrocarbon-bearingformations and the conversion of many of these gases into propellantsabove tripropellants is part of the teaching of this invention. Thefollowing is a list of organic and inorganic propellants that can beproduced from SCF inside hydrocarbon formations to move them out of theformation. These propellant compounds with such positive enthalpies areexplosive in situ when combined. Some of the propellants are too largeand explosive to apply (10CH₂+72NH₄ClO₄+18Al) in situ and others aresmall enough and have a low enough enthalpy to move into the formationporosity to form SCF within the formation permeability. Pure fluorine(F₂) is a corrosive pale yellow gas that is a powerful oxidizing agent.It is the most reactive and electronegative of all the elements andreadily forms compounds with most other elements. Fluorine even combineswith the noble gases, krypton, xenon, and radon. Even in dark, coolconditions, fluorine reacts explosively with hydrogen. In a jet offluorine gas, glass, metals, water and other substances burn with abright flame. It is far too reactive to be found in elemental form andhas such an affinity for most elements, including silicon, that it canneither be prepared nor should be kept in glass vessels. In moist air,it reacts with water to form the equally dangerous hydrofluoric acid. F₂is not a good selection for infusion into hydrocarbon formations.

PROPELLANT SPECIFIC IMPULSE m/s Ideal (I) Field (F) “Field” refers toactual engine firing data.

Solids: (IUS(3) â‰{circumflex over ( )} 3.0 m/s) 10CH₂ + 72NH₄ClO₄ +18Al I = (4) F = 3.33 10CH₂ + 52NH₄ClO₄ + 20Al I = (4) F = 3.40 14CH₂ +72NH₄ClO₄ + 14Be I = (4) F = 3.40 Monopropellants H₂O₂ (hydrogenperoxide) I = 2.40 F = 1.88 N₂H₄ (hydrazine) I = 2.64 F = 2.59Bipropellants ClF₅ + N₂H₄ I = 3.79 F = 3.65 N₂O₄ + N₂H₄ (5) I = 3.96 F =3.47 O₂ + RP-1 (6) I = 4.52 F = 3.73 O₂ + H₂ (SSME) I = 4.97 F = 4.61F₂ + N₂H₄ I = (4) F = 4.28 F₂ + H₂ I = 5.18 F = 4.91 Tripropellants F₂ +H₂ + Li(7) I = 6.89 F = (4) O₂ + H₂ + Be(7) I = 6.91 F = (4) FreeRadicals (Unstable) O₃ + H₂ I = 5.95 F = 5.01 H + H I = 20.89 F = (4)Nuclear Thermal (â‰{circumflex over ( )}3500 K) CH₄ I = 6.00 F = (4) H₂I = 11.00 F = (4)

(1) All chemical energy converted to kinetic energy

(2) Modeled for optimum expansion from 6894 kP to 1.379 kP (1000 psia to0.2 psia, 0.014 atmosphere)

(3) Inertial upper stage—a solid fuel upper stage

(4) No data provided

(5) Ignites on contact. Typical of Titan main engines

(6) Typical of Atlas and Delta main engine

(Reference: Frisbee, Robert, “Ultra High Performance Propulsion forPlanetary Spacecraft,” JPL D-1184, Pasadena, Calif., 1983)

Processing conditions provide the pressure and temperature necessary tocontrol hydrocarbon-bearing formation penetration of SCFs. Nitrogen inthe elemental form was considered to be inert and was even named ozote,which refers to the fact that it is not reactive. Of course nitrogendoes form compounds, but the gaseous form consists of diamers N₂ (2nitrogen molecules bonded together). The nitrogen diamer is very stable,and three nitrogen molecules (N₃) are also relatively stable.

Nitrogen is a major element in organic compounds. Some nitrogencompounds are highly reactive. Trinitrotoluene is TNT or dynamite.Ammonium nitrate is a fertilizer, but was used as the major explosiveingredient in the Oklahoma City bombing. Anfo, or ammonium nitrate andfuel oil mixture, is the primary explosive used in the mining industrybecause it is inexpensive, easy to manufacture, and can be easilymanufactured near the mine site, thus reducing the risks and expensesrelated to the transportation of explosives: nitrates, nitrites, andazides (all nitrogen compounds are either oxidizers or reactives andwill react violently under the right conditions). There are 221 knownnitrogen compounds to select from, depending on hydrocarbon-bearingformation materials and the ability to form a compound in the fuel cellor fuel cell housing. This invention is not limited to nitrogencompounds such as the hydrocarbon-reactive materials. Any compound thatis reactive when exposed to hydrocarbons can be injected through the oilor gas bore hole by providing a supply line of compressed gases fromabove ground and still be within the spirit of this invention. Severalbore holes can be provided to supply multiple potential SCFs througheach bore hole, or SCFs can be formed from the combination of theviolent reactions between non-hydrocarbon materials. It is an objectiveof this invention to penetrate the full volume of the hydrocarbonformation (e.g. propane migrates to the lowest points in the geologicformation and hydrogen migrates to the highest points in the formation,providing full coverage of potential compressible SCFs). As SCFspenetrate the hydrocarbon formation and migrate out hydrocarbons, manyof the natural gases, such as carbon dioxide, nitrogen, hydrogen,propane, and methane, will be compressed into SCFs. The most economicmethod of SCF formation is supplying a single hydrocarbon reactivecompound into the hydrocarbon-bearing formation at a level at which whenit contacts hydrocarbon, it will violently react, compressing thenatural gases, fluids, and materials into the SCF state, penetrating thehydrocarbons for migration out of the formation.

Non-solid fuels include oil and gas (both fuel types have variousvarieties). Crude oil consists of a mixture of petroleum liquids andgases (together with associated impurities) pumped out of the groundthrough oil wells. Oil is a generic term for fluids that are notmiscible with water. In the United States, petroleum is referred topredominantly as oil. Petroleum (from Latin petrus, rock, and oleum,oil) or mineral oil is a thick, dark brown or greenish flammable liquid,which, at certain points, exists in the upper strata of Earth's crust.It consists of a complex mixture of various hydrocarbons, largely of themethane series, but may vary much in appearance, composition, andproperties. Natural gas, which is about 80% methane, with varyingproportions of ethane, propane and butane, is used as a fuel.

Coal is a solid fossil fuel extracted from the ground by mining. It is areadily combustible black or brownish-black rock. It is composedprimarily of carbon and hydrocarbons, along with assorted otherelements, including sulfur.

All these types of fuel are combustible: they create fire and heat.

A fuel cell is not needed in this invention to practice the art of SCFpenetration into hydrocarbon formations. This invention teaches theinfusion of hydrocarbon-reactive compounds into hydrocarbon-bearingformations that violently react (micro-bursts of energy) withhydrocarbons compressing gases (supplied from above ground, a fuel cell,or naturally within the formation) into SCF with nearly 100 percentpenetration into hydrocarbons for extraction. The potential SCF or asmay be natural to the formation and may be any material, including anynumber of reactants or any number of SCFs combined to migratehydrocarbons out of the formation. This invention teaches that water maybe removed from a geologic formation by selecting for it. This inventionteaches that the SCFs can be selected for and combined, if needed, topenetrate the upper or lower regions of the formation. Water adsorbsanhydrous ammonia and can be saturated with anhydrous ammonia (e.g. 25%adsorption), which will react with hydrocarbons when injected into ageologic hydrocarbon formation, forming sCH₂O (supercritical water).sCH₂O has its own unique behavior just prior to going supercritical,because the water dissolves into the formation and is adsorbed,releasing the anhydrous ammonia at the most opportune time. Waste steamfrom a solid oxide fuel cell can have the anhydrous ammonia added to itas the steam is introduced to the hydrocarbon formation.

Infusion of fuel cell produced nitrogen diamers in hydrocarbon-bearingformations where very stable major-gas nitrogen diamers (2 nitrogenbonded together with traces of 3 nitrogen) do not react withhydrocarbons. When combined with minor-gas nitrogen compounds that arehighly reactive (nitrates, nitrites and azides) and with hydrocarbons,they react as a fast, thorough hydrocarbon migration technique toenhance oil recovery in oil fields, completely recovering additionalreserves or prolonging production after primary, secondary, and tertiaryrecovery methods no longer produce oil or gas economically.

SCF increases production efficiency of older fields that can beprolonged by in-situ fuel cell refining of hydrocarbons from withinhydrocarbon-bearing formations. The major gas being infused is verystable nitrogen diamers combined with minor gas highly reactive nitrogencompounds: nitrates, nitrites and azides (all nitrogen compounds areeither oxidizers or reactives and will react violently under the rightconditions). When the minor highly reactive nitrogen compounds(nitrates, nitrites and azides) reach hydrocarbon in formations, even atgreat distances, a micro-violent reaction occurs, compressing stablenitrogen diamers into an SCF with the rapid dissolution rate required topenetrate hydrocarbon-bearing formations as an SCF solvent. Thisinvention teaches that SCF energy can be injected intohydrocarbon-bearing formations when minor traces of highly reactivenitrogen gas compounds reach hydrocarbons; they react violently,compressing the major gas, nitrogen diamers, into the SCF state of scN₂within hydrocarbon cells (natural geologic hydrocarbon formations withinthe non-hydrocarbon micro-porosity), forming a large number ofnucleation sites (orders of magnitude more hydrocarbon penetration bySCFs than would naturally form from nitrogen diamers migration alone)where controlled cell growth occurs. A large and rapid pressure dropimmediately follows SCF states to create the large number of uniformmigration sites. Cells are expanded by diffusion of gas into bubbles(phasing out of their SCF energy state) containing both hydrocarbons andstable nitrogen diamers, further migrating hydrocarbons from thehydrocarbon-bearing formation.

A fuel cell generates electricity from continuously supplied streams offuel and oxidant. The two streams do not mix or burn, but produceelectricity by electrochemical reactions similar to a conventionalbattery. The details of the chemical reactions depend on the type offuel cell, but in all types an electrically charged ion is transferredthrough an electrolyte, which physically separates the fuel and oxidantstreams. The fuel cell thus provides an elegant means of converting thechemical energy of the fuel directly into electrical energy.

Fuel cell assemblies are inserted down hole into a hydrocarbon-bearingformation, regulated by above ground oxygen air supplies down hole, andonly upper lightweight environmentally safe atmospheric air isregulating working gas down hole. Waste gas and steam of the fuel cellare infused into hydrocarbon formations between the bore hole innerdiameter wall and the plurality of infinitely variable seals that sealthe fuel cell assembly within the bore hole. Coal, tar sands,petroleum-contaminated soil, shale beds, and/or oil wells that have lostgas pressure can also have hydrocarbon recovery by this invention'sin-situ method.

Gas-refining in situ is provided by a plurality of bore hole sealsseparating and migrating the fuel cell gases into hydrocarbonformations. This invention teaches an oil well recovery system to targetthe release of nitrogen in the lower formations and steam in the upperformations, which result from down hole fuel cells that release steamand nitrogen. This decomposes the formation, increasing the pressure inthe formation with a violently reacting propellant fuel relative tohydrocarbons pushing out hydrocarbons and water. This multi-sealed fuelcell heat exchanger and conduit vessel can be inserted down hole withinany hydrocarbon-bearing formation: shale bed, oil formation, gasformation, water membrane, coal, contaminated ground, and tar sands, toprovide migration of hydrocarbons from hydrocarbon-bearing formations,consuming the decomposed organics as fuel cell fuels.

Changing the lengths of the intake and exhaust tubes, seal locations andmanifolding separates the system components, positioning them withinhydrocarbon-bearing formation locations, possibly multiple systemsapplied to multiple formations within one bore hole.

A plurality of down hole gas seals are applied at variable depths toisolate and separate gas in the gradient of gases desorbed fromhydrocarbons; the lighter gases are at the top and larger gas moleculesare at the bottom of the bore hole. In addition to gas separation, aplurality of down hole gas seals provides a higher gas pressure, whichis required at the inlet fuel-port of fuel cells to prevent parasiticenergy loss of 4.4 to 7.5 kW/hr's from fuel compressors required in theabsence of pressurized fuel. This down hole gas separation with aplurality of seals is gas refining in situ.

By separating the gases between multiple seals down hole, a blend of allthe gases can be delivered to the fuel cell at 3 to 5 atmospheres ofpressure. Hydrogen is a major component of sour gas, and this inventionteaches that fuel cells can consume the majority of hydrogen to makewater, electricity, and heat in the range of 1200° F. to 1800° F. neededfor further hydrocarbon migration. This invention teaches controllingthe gas separation down hole by the placement of a plurality of sealsregulated through a manifold that separates gases for blending in thefuel cell, which provides the production of nitrogen diamers andnitrogen compounds. The fuel cell computer control is wired to sensorsthroughout the fuel cell for programming precise temperatures andpressures for optimized electrochemical reactions. An elevatedtemperature of 250° F. to 1240° F. fuel cell exhaust temperature isdesirable as a source of heated gas passing through the down hole heatexchanger. This invention teaches production of fuel exhaust gases andpost-processing fuel cell exhaust gases at a range of 250° F. to 1800°F., moving the gases (e.g. steam and nitrogen) into the poroushydrocarbon-bearing formation gases, liquids, and solids, providingcontinuous pressure to move hydrocarbons out and infusion of stablenitrogen diamers (N₂) combined with traces of hydrocarbon-reactivenitrogen compounds into hydrocarbon-bearing formations.

An ideal location for low-pressure oil recovery is where limestone capformations exist above the hydrocarbon formations, because in thesecases a fuel cell in situ below the limestone and within fluidcommunication of the hydrocarbon formation can produce water steampressure and approximately 78% nitrogen waste gas for injection into theformation. Nitrogen diamers infusion into the formation is preferredover steam, because the nitrogen is relatively inert and does not reactwith the hydrocarbons or the formations that the hydrocarbons are heldin. Steam from the fuel cell in contrast can be applied to pressure someformation where the porosity, permeability, and formation materials willtolerate the water and steam pressures. In prior steam injection art,hydrocarbon formations collapse from water-dissolving formations. Thisinvention teaches a down hole fuel cell that converts intake air fromabove ground and hydrocarbons from within the formation to producenitrogen and steam that can be infused into the formation, addingpressure in hydrocarbon formations that have porosity and permeability.This allows hydrocarbons to migrate to nearby bore holes in fluidcommunication with the same formation. Core sample records coulddetermine if the formation can tolerate the addition of steam; nitrogenis always going to be the preferred gas to increase hydrocarbonformation pressure for hydrocarbon migration.

FuelCell Energy, Inc. or Rolls-Royce Fuel Cell systems are more durableand maintainable than the nearest competitors. The Rolls-Royce Fuel Cellis produced by screen printing on low-cost ceramic type materials usingproven production processes and minimal exotic materials. Hybrid fuelcells can easily be made by screen printing other chemical compoundsonto the ceramics; another electrolyte, a catalyst for producingnitrogen compounds, etc. . . . . Profile, size, and weight make solidoxide fuel cells (SOFCs) suitable for distributed generation withpotential for power densities equivalent to gas turbine systems. SOFCshave negligible air emissions (i.e. SOx, NOx, CO, and particulatematter), minimal noise profile, and can be entirely recycled at the endof its useful life. Unique modular SOFC designs can enable fieldchange-out without interruption of supply and enhance support throughstate-of-the-art diagnostic and prognostic systems. Safety in operationis realized because the Rolls-Royce SOFCs system contains less than tenseconds of fuel supply at any time. Durability, low parts count, and theelimination of low durability components gives a realistic design targetof 40,000 hours of operation on a mature product and a 20-year,160,000-hour overall plant life potential. SOFC systems can beconfigured to use existing hydrocarbon-based fuels, i.e. natural gas andliquid fuels, and alternative fuels such as coal gas and bio-mass.

Because fluid and gas molecules can move around quickly, temperaturedifferences do not build up in fluids or gases. Convection is theprocess that distributes the hot gases evenly in a heated hydrocarbonformation. If a mechanical means is used to increase convection, forexample, a pump (or compressor) or fan, the process is called forcedconvection. Forced convection is an option used in this invention toheat the hydrocarbon formation when natural convection no longer yieldsa gas: a compressor circulates working gases continuously along the fuelcell to carry away excess heat. Conduction processes may occur in theliquids and gases, but for these fluids, it is difficult to preventmotion of parts of the gases and liquids; once molecules are in motiontransporting heat, they are converted to circulating convection-workinggases and liquid.

If heating moves molecules far enough apart, the critical temperaturewill be reached, at which point the influence of attractive forces isalmost completely overcome. The molecules are no longer constrained. Themolecules, now a gas, would be able to move about freely and completelyfill the volume available within formation porosity. Gases arecharacterized by their sensitivity to changes in temperature andpressure. In the kinetic gas theory, gas pressure increases when a gasis enclosed in a fixed volume and its temperature is raised. The gaspressure is the measure of the average speed at which the gas moleculesmove about. SCFs form when the rate of a gas compression is high enoughto saturate neighboring molecules without volume increases (a temporaryenergy potential stored). When the temperature is raised, the averagespeed of the particles increases, as does their energy. Nitrogen diamersSCFs strike the hydrocarbon formation walls at higher speed, saturatinghydrocarbons with energy potential, and thus exert a larger forcebetween the wall and hydrocarbons, migrating the hydrocarbons at greaterdistances faster. Reference to hydrocarbon-bearing formations mayinclude any hydrocarbon formation and does not limit this invention tooil and gas recovery.

This invention teaches that convective currents can be added to anyhydrocarbon formation by sealing the well hole with a plurality of sealsthat seal gas pressures down hole during heating, which will increasethe pressure and penetration of working gas, “stripping” hydrocarbonsfrom hydrocarbon-bearing formations. In this invention, gas compressorsor supply lines can be inserted within the plurality of seals, forcingconvection-working gases to cycle back to the heat source within thehydrocarbon formation, increasing distance penetration of working gases.Hydrocarbon-bearing formations have a wide range of pore sizes, whichmay require forced convection in situ cycled between the pluralities ofdown hole seals. This invention teaches that holding the gases within anatural or forced convection heat until the heavier organics aredecomposed down hole can process all the organics and gases in thehydrocarbon formation, meeting environmental emission requirements. Thisis in-situ refining.

Fuel cell intake air is vacuumed, blown, or compressed mechanically tomove atmospheric air through the fuel cell to deliver oxidants. Thisinvention teaches that heating the working gas from hydrocarbonformations from fuel cell waste heat through a down hole heat exchangerprovides all the fuel to produce electricity, steam, and nitrogen.Intake air is vacuumed against the oxygen adsorption site of a fuelcell, providing oxygen to the fuel cell. A very simple down hole in-situfuel cell system would require an air blower or compressor at aparasitic loss because it would have to mechanically move atmosphericair through the fuel cell to deliver oxygen from air. The down hole heatexchanger on the fuel cell housing provides heat to decomposehydrocarbons for fuel gases, depending on the fuel cell type. Solidoxide is the preferred fuel cell type because it can react with a familyof hydrocarbon sourced gases—a hybrid combination of different types offuel cells can be applied to refine decomposed hydrocarbons. Thisinvention teaches that an optional manifolding system and adsorbentsspecies can be applied and customized to process difference ratios oforganic species available across an infinitely variable range offormations. Any number of these heat exchanger bore hole sealed systemscan be applied in the same bore hole, which is governed by the thicknessand number of formations. Steam can be applied to damage and collapse anupper formation to increase the sealing of the lower formation.Collapsing formations, whether below, above, or around the bore hole, isa professional judgment of the geologist managing the hydrocarbonproduction. An air supply, fuel cell, and sealed heat exchanger plumbedwith conduit to infuse nitrogen into the formation and release steam toatmosphere or infusion into a formation are all that is needed to makethe system work.

The oxygen required for a fuel cell comes from air mechanically moved tothe fuel cell. A reformer turns hydrocarbon or alcohol fuels intohydrogen, which is then fed to the fuel cell. Unfortunately, reformersare not perfect. They generate heat and produce other gases besideshydrogen. They use various devices to try to clean up the hydrogen, buteven so, the hydrogen that comes out of them is not pure, and thislowers the efficiency of the fuel cell. Methanol is a liquid fuel thathas properties to gasoline. It is just as easy to transport anddistribute, so methanol may be a likely candidate to power fuel cells.

Five major types of fuel cells exist, and each has a different operatingtemperature, as follows: Fuel cells such as polymer electrolyte membranefuel cells, 75° C. (180° F.); alkaline fuel cells, below 80° C.-75° C.(180° F.); phosphoric acid fuel cells, 210° C. (400° F.); moltencarbonate fuel cells (MCFC) 650° C. (1200° F.); SOFCs, 800° C.-1000° C.(1500° F.-1800° F.). MCFCs and SOFCs have operating temperatures highenough to desorb and strip hydrocarbon bearing formations at 1200° F. to1800° F.

MCFC uses a carbonate-salt-impregnated ceramic matrix as an electrolyte.Because MCFCs operate at 800° F., they are best suited to large,stationary applications. Yet they potentially have the most to gain, asthey operate at 85 percent efficiency with cogeneration. They will beespecially useful in hospitals, hotels, or other industrial applicationsthat require electricity and heating (or cooling) around the clock.

SOFCs are best suited for large-scale stationary power generators thatcould provide electricity for factories or towns. SOFCs use aprefabricated ceramic sandwich between electrodes. Like MCFCs, theyoperate at higher temperatures (about 1000° F.) and make excellentco-generation devices for industrial applications where high temperaturesteam is required.

-   www.eere.energy.gov/hydrogenandfuelcells/fuelcells/types.html

One of the characteristics of an SOFC is that the fuel must be injectedinto the cell chamber at relatively high pressure of three to fiveatmospheres. When using gaseous fuels, this requirement for fuelcompression requires significant power, which must be considered part ofthe system when calculating net power output. The fuel compressor is aparasitic load reducing fuel efficiency. Two examples: a Capstone®Turbine C30 generates 30 kW/hr and would require a minimum of 4.4 kW/hrfuel compressor, compared to model CapStone® Turbine C60, whichgenerates 60 kW/hr and would require up to a 7.5 kW/hr fuel compressor.

Synthetic molecular sieves are porous, crystalline alumino-silicatesthat function much like a natural sieve; they adsorb some molecules andreject others. The absorption and desorption are completely reversible.Custom synthetic molecular sieves are applied in above ground modem oilrefineries as molecular gas separator beds. In contrast,hydrocarbon-bearing formations are a natural composite of severalnatural molecular sieve species, which in a past natural environmenthave adsorbed a variety of organic hydrocarbons. In addition, theorganic molecules physically imbedded in the natural hydrocarbon-bearingsieves have adsorbed gas molecules (e.g. hydrogen, methane, carbondioxide). The molecular variety of organics in hydrocarbon-bearingformations is related directly to several natural molecular sievespecies. Since molecular sieves adsorb materials through physical forcesrather than through chemical reaction, they retain their originalchemical state when the adsorbed molecular is desorbed. There are fivetypes of adsorption/desorption cycles:

-   1. Thermal swing cycles involving rising desorption temperatures,-   2. Pressure or vacuum swing cycles involving decreased desorption    pressures,-   3. Purge-gas stripping cycles using a non-adsorbed purge gas,-   4. Displacement cycles using an adsorbable purge to displace the    adsorbed material, and-   5. Adsorptive heat recovery, using the retained heat of absorption    to desorb certain molecules (e.g., water).

This invention teaches applying all five of the above-mentionedadsorption/desorption cycles to produce nitrogen compounds that reactviolently with hydrocarbons.

Yet a further drawback of the prior art is that the working gas requiredto recover hydrocarbons was not a combined non-reactive and reactivenitrogen compound. Stationary hydrocarbon-bearing formation requiresworking gas penetration radially from the bore hole into the depth of ahydrocarbon-bearing formation rather than the limits of conductive andradiant heat limited to the immediate proximity of the heat source.Hydrogen is released from the hydrocarbon-bearing formation when heated.This invention teaches methods of pressuring the hydrogen into theporous hydrocarbon-bearing formation, penetrating thehydrocarbon-bearing bed with a hot working gas at greater distances andvariable pressures.

The alternative recovery process involves in-situ operations whereinbore holes drilled into subterranean hydrocarbon formations vertically,horizontally, and at angles are combined with various apparatus intendedto recover oil and/or gas from the surrounding hydrocarbon-bearingformations.

To be considered economically feasible, a recovery system must becapable of functioning when applied to hydrocarbon-bearing formationslocated at any depth, even at the most minimum of depths such as whenthe overburden may extend only five feet in depth, thereby avoiding thenecessity of drilling bore holes of extreme depths. Additionally, aviable system should integrate cogeneration systems that manage heat andshould, once in place and operational, be capable of producingcommercially acceptable electricity and water from the gas for anextended period of time.

In accordance with the present invention, the working fluid can beheated. Thermal chemical reaction will not occur, and catalytic reactionwill be easier to manage, since the working gas physically moves fromone location to the other by pressure and heat. Further, in someembodiments the working gas contains multiple gases: hydrogen, helium,propane, methane, and carbon dioxide.

Propane gas is affected by gravity, moving downward, and can be releasedinto the drill hole to penetrate the hydrocarbon pores, providing acatalyst that can be added to start a chemical reaction within the borehole and then substantially removed. Some catalytic reactions need aneven distribution of catalyst, and this technology can provide anaggregate effect, gathering density, or a uniform effect. Prior art doesnot teach uniform gradient or thermal processing or reactive gas thatcompresses working gases into SCFs that saturate and then migratehydrocarbons at any distance.

DESCRIPTION OF THE RELATED ART

Prior enhanced oil recovery projects may involve gas re-injection,carbon dioxide (CO₂) flooding, or various horizontal drillingtechniques.

Prior art has three stages of oil field development: primary recovery,secondary recovery, and tertiary recovery. Primary recovery produces oiland gas using the natural pressure of the reservoir as the driving forceto push the material to the surface. Wells are often stimulated throughthe injection of fluids, which fracture the hydrocarbon-bearingformation to improve the flow of oil and gas from the reservoir to thewellhead. Other techniques, such as pumping and gas lift, helpproduction when the reservoir pressure dissipates. Secondary recoveryuses other mechanisms—such as gas reinjection and water flooding—toproduce residual oil and gas remaining after the primary recovery phase.Tertiary recovery involves injecting other gases (such as carbondioxide) or heat (steam or hot water) to stimulate oil and gas flow,producing remaining fluids that were not extracted during primary orsecondary recovery phases.

SCF recovery methodology eliminates the prior art's three stages:primary, secondary, and tertiary. SCF methods are intended for brand newbore holes (and pressure depleted formations) in hydrocarbon formationswhere SCFs and heat from fuel cells can substantially refine petroleum,produce clean natural gas in situ, apply heat to break methane intohydrogen, and completely migrate hydrocarbons in situ in a singleprocess.

SUMMARY OF THE INVENTION

The process presented herein produces gases and fluids that areseparated down hole and regulated to decompose the maximum amount of theorganics in hydrocarbon formations by convection working gases thatmigrate reactive gases into contact with hydrocarbons, compressingsurrounding gases into SCFs.

The process presented herein produces gases and fluids that areseparated down hole by a fuel cell and regulated to decompose themaximum amount of the organics in a depleted oil well bore hole bymoving air into the fuel cell as it heats and decomposes convectionworking gases, providing steam and nitrogen to pressure fluids out ofthe oil formation.

Accordingly, one of the objects of the present invention is to providean improved process for desorbing the gasification of oil in situ,including the controlled application of heat within a bore hole from afuel cell to increase steam pressure and provide nitrogen as a workinggas to pressure formations filled with oil. Some formations will requiresteam to press the oil out of the formation, and other formations willbe damaged from the steam. This invention teaches that the nitrogen,steam, and other exhaust gases from the fuel cell can be applied toincrease pressure in the formations by infusion directly into theformation from the fuel cell. Fuel cells can infuse nitrogen alone intoformations that are damaged or would be damaged by steam injectionmethods. Other residue gases decomposed from heat absorption radiallyaround the fuel cell housing will be applied as fuel cell fuel orreinjected into the formation as working fluid when the gas availablematches the formation survivability.

With these and other objects in view that will more readily appear asthe nature of the invention is better understood, the invention consistsin the novel process and construction, combination and arrangement ofparts hereinafter more fully illustrated, described and claimed, withreference being made to the accompanying drawings in which:

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic view of an SCF cell in a hydrocarbon-bearingformation;

FIG. 2 is a vertical elevation, partly in section, and above-groundsystems partly in diagram of an oil hydrocarbon-bearing formation of thepresent invention;

FIG. 3 is a diagrammatic schematic view of an SOFC fuel cell diagram;

FIG. 4 is a table of fuel cell types, fuels, temperatures, electrolytes;

FIG. 5 is a cross-sectional elevated bottom view of a heat exchanger forinsertion in a hydrocarbon-bearing formation bore hole;

FIG. 6 is a cross-sectional elevated top view of a heat exchanger forinsertion in a hydrocarbon-bearing formation bore hole;

FIG. 7 is a cross-sectional side view of a heat exchanger for insertionin a hydrocarbon-bearing formation bore hole;

FIG. 8 is an end sectional view of a heat exchanger for insertion in ashale formation bore hole;

FIG. 9 is a partially exploded view of a heat exchanger bore hole;

FIG. 10 is an elevated top end view of a heat exchanger core forinsertion in the heat exchanger of FIGS. 5-7;

FIG. 11 is an elevated bottom end view of a heat exchanger core forinsertion in the heat exchanger of FIGS. 5-7;

FIG. 12 is a cross-sectional elevated top view of a heat exchanger;

FIG. 13 illustrates a typical chemical reaction profile that producesinstances of SCF cells;

FIG. 14 is a graph illustration of the critical point and pressure andtemperature above the critical point where liquid and gas phase into anSCF even in varied densities.

FIG. 15 illustrates the electrochemical synthesis of hydrogen peroxideon anthraquinone-modified electrode.

FIG. 16 illustrates a simple ammonia SCF system in a casing cemented ina hydrocarbon formation borehole, which is sealing the outside casing.

FIG. 17 illustrates a graphite monolithic brick with fibrous ends.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Referring now to the drawings, particularly FIG. 1, the presentinvention relates to an in-situ system for recovering hydrocarbons fromhydrocarbon formations. In hydrocarbon-bearing formations in FIG. 1,there are two dominant structures: hydrocarbons 100 and the porousnon-hydrocarbon formation 101 that structurally form the support of thehydrocarbon-bearing formation 110. Infusion of stable nitrogen diamers(N₂) 102 combined with traces of hydrocarbon-reactive nitrogen compoundsand anhydrous ammonia (NH₃) 103 into hydrocarbon-bearing formations 110,which violently react (micro-bursts of energy) with hydrocarbons methane(CH₄) 105, compress nitrogen into SCF cells 106 of supercriticalnitrogen diamers (scN₂) 104 with orders of magnitude more penetrationinto hydrocarbons than would naturally form from nitrogen diamers 102migration alone. Hydrocarbons can be fully saturated with SCF, whichmigrate hydrocarbons out of formations, even at great distances from theregulated fuel cell source. When potential supercritical gases andfluids are already naturally in situ, carbon dioxide (CO₂), 107, water(H₂O), 108, (H₂) 109 within the formation 100, only ahydrocarbon-reactive compound anhydrous ammonia (NH₃) 103 needs to beinfused into the hydrocarbon formation 110.

Systems are integrated together into a more efficient cogenerationprocess: in-situ shale fuel production, electric generation, mechanicalturbine energy (electromagnetic generator), and water making. A heatexchanger is designed with three functions: a recuperator/fuel heater,intake air heater, and downhole shale working gas heater. This heatexchanger is connected to the hot gas side of a microturbine andinserted into an organic rich shale borehole to heat working gases inthe shale. Inverse rotation water is potable and equal to rain quality.

Heat and fuel path: Hot natural gas desorbed from shale at ˜3 to ˜6atmospheres of pressure passes through a recuperator/fuel-heater to aFuel Cell Energy® fuel cell, while air is simultaneously, filtered,compressed through the Capstone turbine, inverse rotated for watermaking, heated in a recuperator, and compressed into the fuel cell.Solid Oxide fuel cell (SOFC) generators provide 1500-1800° F. steam todrive the hot-gas turbine blade, which compresses atmospheric air intothe fuel cell at the opposite end of the turbine. All or part of thehybrid system can be inserted downhole. Fuel cell water is industrial orfarm irrigation quality.

In FIG. 2 is a heat exchanger assembly, generally designated 12, whichis lowered into a bore hole 14 drilled into a hydrocarbon-bearingformation 15 located beneath overburden 16. Exhaust 4 is connected tothe heat exchanger 12 in the hydrocarbon-bearing formation 15 andexhaust 4 is an exhaust out of the bore hole heat exchanger 12 vented toair. Exhaust 4 out of the bore hole 14 can be restricted to increase ordecrease the temperature of the heat exchanger 12 and the velocity andregulation of air movement out of the heat exchanger 12 can form anadiabatic gas stream into the heat exchanger 4, which minimizes thecontact the gases have with the conduit 20 inside diameter beforeentering the inlet port 21 of the heat exchanger 12. This adiabaticcontrol is important because of the potential depth of the bore hole 14.This invention teaches adiabatic gases can travel greater distancesbefore losing heat to the conduit connected to the inlet port of theheat exchanger 12.

In FIG. 2, intake air is vacuumed against the oxygen adsorption site ofa fuel cell in heat exchanger 12 within bore hole 14, providing oxygento the fuel cell 98. A very simple down hole in-situ fuel cell systemwould require an air blower or compressor 99 at a parasitic loss becauseit would have to mechanically move atmospheric air through the fuel cell98 to deliver oxygen from air. The down hole heat exchanger 12 on thefuel cell heat exchanger housing 12 provides heat to decomposehydrocarbons for fuel gases depending on the fuel cell type. Solid oxideis the preferred fuel cell type because it can react with a family ofhydrocarbon sourced gases—a hybrid combination of different types offuel cells can be applied to refine decomposed hydrocarbons. Thisinvention teaches an optional manifolding system and adsorbents speciescan be applied and customized to process different ratios of organicspecies available across an infinitely variable range of formations. Anynumber of these heat exchanger bore hole sealed systems can be appliedin the same bore hole, which is governed by the thickness and number offormations. Steam can be applied to damage and collapse an upperformation to increase the sealing of the lower formation. Collapsingformations, whether below, above, or around the bore hole, is aprofessional judgment of the geologist managing the hydrocarbonproduction. An air supply, fuel cell, and sealed heat exchanger plumbedwith conduit to inject nitrogen into the formation and release steam toatmosphere or inject into a formation are all that are needed to makethe system work. Any natural geologic hydrocarbon formations that haveporosity and permeability, which allow hydrocarbons to migrate, aretarget locations for this invention. An ideal location for low-pressureoil recovery is where limestone cap formations lie above the hydrocarbonformations, because in these cases a fuel cell in situ below thelimestone and within fluid communication of the hydrocarbon formationcan produce water steam pressure and 78% nitrogen waste gas forinjection into the formation. Nitrogen injection into the formation ispreferred over steam, because the nitrogen is relatively inert and doesnot react with the hydrocarbons or the formations that the hydrocarbonsare held in. Steam from the fuel cell in contrast can be applied topressure some formations in which the porosity, permeability, andformation materials will tolerate the water and steam pressures. Inprior steam injection art, hydrocarbon-bearing formations collapse fromwater dissolving the formations' non-hydrocarbon porous structures. Thisinvention teaches a down hole fuel cell that converts intake air fromabove ground and hydrocarbons from within the formation to producenitrogen and steam that can be injected into the formation, addingpressure in hydrocarbon formations that have porosity and permeability,which allow hydrocarbons to migrate to nearby bore holes in fluidcommunication with the same formation. Core sample records coulddetermine if the formation can tolerate the addition of steam wherenitrogen is always going to be the preferred gas to increase hydrocarbonformation pressure for hydrocarbon migration. In some formations, thereare multiple layers of hydrocarbon formations, perhaps above and below alimestone layer, which could have the steam applied to the upper layerand nitrogen applied to the lower layer from the same fuel cell sourceor fuel cells adjacent to the formation. As the depth of the formationincreases, the conduit and tubing can be cobalt stainless steel withinsulation of the Esterline silicone insulating surface types, whichincludes making the seals out of silicon types for heat survivabilityand petroleum resistance.

Pressurized air needed by the SOFC can be provided by the compressor,the SOFC can act as the system combustor, and the exhaust from the SOFCcan drive the compressor and a separate generator. The fluid streamcontains gases and/or liquids. Siemens Power and Franklin Fuel Cell areleading the industry in SOFC fuel cells. For the purposes of thisinvention, the Rolls-Royce fuel cell was selected for its innovative useof ceramics to connect the circuit, with greater lifetimes anticipated.Tube fuel cells will fit down hole in this invention's heat exchanger inFIGS. 5-12. The convection gases would be consumed by the tubular arrayfuel cell with the Franklin, Rolls-Royce, Siemens, FuelCell Energy,Inc., or other suitable fuel cell. In FIG. 4 table, the six basicdifferent types of fuel cells are listed to evaluate and match fuels tothermal requirements in situ to target hydrocarbon formations. A furtherobjective of this invention is to separate the gases and select the bestgas for each fuel cell type until most of the desorbedhydrocarbon-bearing gases are consumed by a fuel cells matched to thegas types (e.g. hydrogen, methane, carbon dioxide, and carbon monoxide).Adjustments can be made in the fuel cells to supply the ratio of gasesbest for hydrocarbon gas infusion and in-situ refining technology.During normal operation, air enters the compressor and is compressed to˜3 atmospheres. This compressed air passes through the fuel cell, whereit is preheated, and then enters the SOFC. Pressurized fuel from thefuel pump also enters the SOFC and the electrochemical reactions takesplace along the cells. The hot pressurized exhaust divides the SOFC intothree streams: steam, nitrogen diamers, and nitrogen compounds, whichmigrate to hydrocarbon formations. Electric power is generated by theSOFC (dc), which is the most efficient use of this system.

Fuel supply 9 has to be pressurized between ˜3 to ˜5 atmospheres. A fuelcompressor is required if gas is low pressure.

As shown most clearly in FIGS. 5-11, the cylindrical 30 of the heatexchanger assembly 12 defines an enclosed interior 41 bounded by a topwall 42 and bottom wall 43. The purpose of the heat exchanger 12 is todeliver a substantially constant amount of the heat to the surroundinggases and liquids decomposing hydrocarbon from formation 18; a close fitexists between the periphery of the heat exchanger housing 44 and thewall 46 of the bore hole. As an example, the heater housing may be teninches in diameter and disposed within a 12-inch bore hole, therebyinsuring a definite but minimal lateral clearance between. Special heatresistant stainless alloys coated with Esterline silicon insulation,carbon foams developed by Oak Ridge National Labs, coal-based foam(www.CFoam.com Super Carbon Foam®), high-temperature ceramics, andcarbon graphites in refining quenching towers are used for theconstruction of the heater assembly 12. These materials have been foundto satisfactorily withstand exposure to temperatures of 2500° F. for anextended period. The seal and conduit can be coated with insulationmaterials from Esterline Corporation in Kirkland, Wash., USA to managethe thermal processes in situ. The same technology applied in thehydrocarbon-bearing formation can be applied any depth and separated atany depth for in-situ pressure from fuel cell nitrogen and/or steam. Anyof the surfaces of heater assembly 12 can be fuel cell components,because simple screen printing is applied to make SOFCs. The fuel cellheater assembly 12 is an integrated refinery in situ, which combines therefining components of adsorbent molsieves, catalysts, and fuel cellcomponents.

In FIGS. 2, 5-12, conduits communicate between the ground surface 19 andthe interior 41 of the heat exchanger 12 housing 47 and include sixfuel-gas supply conduit 50 terminating in a suitable gas manifold aboveground 13 (FIG. 2), heat exchanger manifold 49 juxtaposed the housingbottom wall 41, conduit 57, and six plugs 58. To separate the gases downhole, the working gas is fuel, a plurality of portholes 51-56 is placedevery 60 degrees around the centerline of rotating conduits 50. Conduithousing 57 has one of the six different holes 51-56, providing an intakefor hydrocarbon-bearing working gas (fuel) generally separated bygravity gradient. These conduits 50 rotate within the housing 57 toreceive different gases for blending in fuel cells or other uses aboveground or in the bore hole. For example: intake port 51 would registerwith the single port in housing 57 port 51, providing only hydrogen gasin that conduit; in contrast, bottom port 56 and inlet port 56 onconduit 50 register to provide the intake of natural propane or carbondioxide. Exhaust air vents through six annular vents 60. Vents 60 arediagrammed in FIG. 2 as exhaust 4 through conduit 3. Fuel cell hotexhaust gas 4 is provided an insulated conduit 20 (FIG. 2), which is influid connection to conduit 45 in heat exchanger 12. All six conduits 50lead from a heat exchanger assembly 12 up to manifold 13 (FIG. 2),providing the potential to blend fuels in the fuel system (FIG. 2),which distributes fuel to a fuel cell only. A group of fuel cells eachconsuming the gas as its catalyst and electrolytes are designed toadsorb into a fuel conversion to electricity (this is a refining processwith groups of fuel cells each consuming what would otherwise be a wastegas), and other distribution or power systems. For maximum gasseparation monitoring, a sensor 25 (FIG. 2) is placed just below thehydrocarbon-bearing formations 18 to monitor gas-leaking from theprocess. Hydrogen will leak out and this sensor 25 provides the rate tominimize, if not eliminate, the loss of fuels. On conduit 3 (FIG. 2), abutterfly valve 16 is provided to control the exact temperature of theheat exchanger 12; valve 16 provides the exhaust gas stream maintainingit in an adiabatic state by controlling the rate of gas pull throughconduit 3 and minimizing the heat loss in the exhaust gas 4 from turbineor other heat sources. Intake conduit 45, housing 57, tube 61, heatexchanger end cap 47 are positioned concentrically within thehydrocarbon-bearing formation 18 bore hole 14 relationship by a suitableplurality of gas seals (not shown) that are infinity adjustable to sealgas clearances between tube 61 and hydrocarbon-bearing formation 18 borehole 14. The fuel cell circuit will be described hereinafter, followinga description of the process of the invention.

In FIGS. 2 and 5-12, continued maintenance of a working gas temperaturein the range of 150° C. to 1371° C. and gas pressure at 3 to 7atmospheres progressively expands the radius of this fuel supply 9 withthe mass of volume of the working desorption gas constantly increasingin an amount proportionate to the increase in the radius of the reactionzone. It is projected that as long as the pressure of the convectionheated working gases does not leak out of a natural fracture in thehydrocarbon-bearing formation 18 or break through the top of thehydrocarbon-bearing formation 18 (FIG. 2), there is no known limit. Thisinvention teaches that horizontal bore holes can be desorbed by sealingin the heat exchanger with the plurality of seals on the outer diameterof heat exchanger 12 assembly, which includes tube 61 and housing 47 toseal the gas in. It is understood that the heat exchanger can be madeany dimension, length, and diameter to desorb very thickhydrocarbon-bearing formations and very thin surface formation. Thisplurality of seals (not shown) is also used to close off underwaterstreams where fractures exist. Seal can be manufactured from simpleexpansion fluid-filled bladders wrapped around housing 47 and tube 61 toseal off bore hole 14, electrically contracted piezoelectric waferfilled expansion tubes/seals, and bipropellant foams. This inventionteaches a range of temperatures that match the hydrocarbon-bearingformation organics potential to desorb.

In FIGS. 2, 5-12, as the gas moves through the hydrocarbon-bearingformation, it ultimately reaches the outer tube 61 and passes into oneof the six inlet ports 51-56 on rotating conduit 50, the gas space 62 asdefined by the thin, cylindrical space intermediate to the heatexchanger 12 surface 44 and bore hole wall 14. The vertical limits ofthis gas space are restricted to the height of the heater assembly bythe inclusion of a plurality of horizontal seal members 64 (FIG. 2),spanning the expanse of the bore hole 14 immediately atop the heatexchanger top wall 63. These air impervious seals, coupled with the borehole floor 17, are seen from FIG. 2 to restrict all gas directed fromthe reaction zone into the gas space 62 surrounding the heat exchangerassembly at the external periphery 65. Convection working gas volumes inthe desorbed hydrocarbon-bearing fuel supply 9 will be added to by theheat and pressure regulation over time. Convection heated working gasand fluids will form a gradient from gravity in the poroushydrocarbon-bearing formation 9 and the space 62 around the heatexchanger housing. Hydrogen is more abundant in hydrocarbon-bearingformations than prior art tested for. The hydrogen is the smallestmolecule to seal into space 62 and will be the top gas inlet port 51lets pass in. The rotating conduits 50 can be turned to register theinlet ports 51-56 to the ports 51-56 in housing 57. Conduits 50 can berotated from above ground on the manifold regulating gases. Pressure andthe mix of gases in fuel supply 9 are controlled to decompose thecrosslinked organics to their lowest molecular weight material. Conduits50 are heated by annular vent 60 and turbine exhaust gas intake tube 45to keep the fuel supply and separation conduits 50, 57 clean. Exhaustgas 4 can have heat added by burning some fuel 9 above ground if acogeneration element of the above-ground hybrid heat source is not at ahigh enough temperature. Water jet cutting in the bore hole 14 canexpand the space 62 to any size required, and the plurality of seals canbe any size and shape to accommodate the shape and size of the cavitycut in a greater radius than the bore hole. Water-jets can also precut5- to 10-centimeter diameter small bore holes (not shown) around thelarger bore hole 14 if added convection working gas can make ahydrocarbon-bearing formation more productive or venting a pocket oflightweight gas has formed at a radial distance too great for releaseout of port 51-56.

In FIG. 3 water production during cogeneration is an additionalcogeneration function. Water making from microturbine compressed airinverse rotation is provided by vacuuming intake air through amicroturbine air filter 21 a; passing the filtered air through a turbineblade 22 b; and then compressing the atmospheric air through an inverserotation water separator 21 before entering the fuel air mixing chamber26. 99.9% of the water is separated from air and drains out line 23. Atthe high end, 600-CFM to 900-CFM (Cubic Feet per Minute) of air iscompressed through the water separator 21 eliminating parasitic losses(100% loss) that would result from a compressor “exclusively” being usedto compress air for the same inverse rotation water separator 21 forwater production. Fuel cells 27 consume hydrogen from the shale and aportion of the oxygen from the microturbine 28 intake air 29 providingwater and electricity.

In FIG. 12 water production can be provided for a few centuries, becausewater membrane filtration is the final use of abandoned spent shalebeds. Shale water membrane filtration is provided by passing brackishwater through porous activated shale beds stripped into a sphere (watermembrane filtration) bed 75 and a stripped tube (water membranefiltration) bed 76 stripped of organics by pressurized hydrogen workinggas convection heat desorption and SCFs. Horizontal shale drilling hole70 enables the total system heat exchanger 12 to be inserted within aborehole 70 where water-jet vertical borehole cuts 71 in the shaleprovide the intake and exhaust air from aboveground. Horizontalboreholes 70 in shale provide a shale water pipe for centuries ofgravitational fed water membrane filtration; recharging potable waterthrough activated spent shale. Several horizontal boreholes can drainpotable water into a common transport pipe. Several sets of horizontalboreholes 70 can be structured over each other in parallel positions toprovide a cascade filter system and aid in stripping the shale. In thickshale beds these horizontal boreholes 70 can be as large in diameter aslarge highway automobile tunnels (boreholes 70).

A catalyst, chemical decomposer, scrubbers, and other yet unknown gas,fluids, or powder materials can be forced down hole into space 62through conduit 50. Adsorption materials can be modified within the heatexchanger to produce any chemical compound that hydrocarbons can produceaboveground.

In FIG. 13 a typical chemical reaction profile is illustrated. Inchemistry an activated complex is a transitional structure in a chemicalreaction that results from an effective collision between molecules andthat persists while old bonds are breaking and new bonds are forming. Itis therefore a range of molecular geometries along the reactioncoordinate: When molecules collide, some of their kinetic energy isconverted into potential energy within the colliding molecules. Ifenough energy is converted, the old bonds become sufficiently distortedfor the colliding molecules to form an activated complex. New bonds canthen begin to form. In this brief interval of bond breakage and bondformation SCF can form, the collision complex is in a transitionalstate. Some sort of partial bonding exists in this transitionalstructure. The exact structure of this complex is often difficult todetermine, but is important to understanding the mechanism of a reactionthat provides SCF within low porosity hydrocarbon formations.

Referring now to the drawings, particularly FIG. 14, the presentinvention relates to oil and gas recovery applying SCFs. In FIG. 14, thephase boundary between liquid and gas does not continue indefinitely.Instead, it terminates at a point on the phase diagram called thecritical point. This reflects the fact that, at extremely hightemperatures and pressures, the liquid and gaseous phases becomeindistinguishable.

Critical variables are useful for rewriting a varied equation of stateinto one that applies to all materials so chemists can select the bestpotential SCF.

On a PV diagram, the critical point is an inflection point. Thus:

$\left( \frac{\partial P}{\partial V} \right)_{C} = 0$$\left( \frac{\partial^{2}P}{\partial V^{2}} \right)_{C} = 0$

For the van der Waals equation, the above yields:

$P_{C} = \frac{a}{27\; b^{2}}$ v_(C) = 3 b$T_{C} = \frac{8\; a}{27\;{bR}}$

If any liquid is heated in a sealed system, the liquid expands and thevapor above the liquid becomes denser due to evaporation. If heating iscontinued or pressure is applied, it is possible to reach the criticalpoint at which the vapor phase is as dense as the liquid phase, and asupercritical phase is achieved. This supercritical phase, at and abovethe critical point, is unique in having both gas-like and liquid-likeproperties.

SFC Examples P_(c), Fluid T_(c), ° C. atm d* Air — −140.5 37.71 — Carbondioxide CO₂ 31.3 72.9 0.96 Nitrogen N₂ −147 33.9 — Nitrous Oxide N₂O36.5 72.5 0.94 Ammonia NH₃ 132.5 112.5 0.40 Methane CH₄ −82.7 45.96 —Pentane n-C₅ 196.6 33.3 0.51 Aliphatic alcohols n-C₄ 152.0 37.5 0.50Dichlorodifluoromethane (R12) CCl₂F₂ 111.8 40.7 1.12 Trifluoromethane(R23) CHF₃ 25.9 46.9 — Water H₂O 374 220.6 Xenon X_(e) 16.5 58.4 —*density in g/ml at 400 atm

In chemistry and condensed matter physics, a critical point specifiesthe conditions (temperature, pressure) at which the liquid state of thematter ceases to exist. As a liquid is heated, its density decreaseswhile the pressure and density of the vapor being formed increases. Theliquid and vapor densities become closer and closer to each other untilthe critical temperature is reached, at which the two densities areequal and the liquid-gas line or phase boundary disappears. The criticalpoint in FIG. 14 phase diagram is at the high-temperature extreme of theliquid-gas phase boundary. SCFs have densities approaching those ofliquids together with the mass transport properties of gases. Thiscombination gives them unique properties as solvents for chemicalprocesses. In particular, complete miscibility of gases and substratescan be achieved at relatively high concentrations. The triple point iswhere gas, liquid, and solids coexist and is typical of brand-newformations that are being drilled into. The triple point is the point atwhich all hydrocarbon formations are moving toward during decliningproduction (pressure) in a system at rest.

SCFs

These fluids have densities and diffusivities similar to liquids butviscosities comparable to gases.

Mobile Density Viscosity Diffusivities Phase (g/ml) (poise) (cm²/sec)Gas ~10⁻³ 0.5-3.5 (×10⁻⁴) 0.01-1.0 SCF 0.2-0.9 0.2-1.0 (×10⁻³)  0.1-3.3(×10⁻⁴) Liquid 0.8-1.0 0.3-2.4 (×10⁻²)  0.5-20 (×10⁻⁵)

FASTBLOCK® 100 SERIES compounds are ready-to-use, moisture-curablefirewall sealants for high-vibration areas. These one-part, non-ablativesealants cure to tough, durable elastomers upon exposure to air. Thematerials adhere well to metals, composites, paints, and most othercommon substrates without the use of primers or special surfacepreparation. Esterline Corporation of Kirkland, Wash. State, USAprovides FASTBLOCK® 100 SERIES sealants, which have a paste consistencythat makes them effective on vertical and overhead surfaces. 100 SERIES,300 SERIES and 800 SERIES materials are applied to combine fuel cellelements with intake and exhaust conduit tubing and seals. FASTBLOCK canbe applied to cobalt stainless steel, providing an easy method to bendpipe, coat pipe and maintain pipes to adapt these in-situ fuel cells todown hole heated environments.

In structures of this invention, where FASTBLOCK® will not meet demands,high-strength bonding of dissimilar materials, particularly withhigh-performance ceramics to low- and high-density metals for in-situoil refining, chemical processing facilities, petroleum drilling and,and production. TII (TECHNOLOGY INTERNATIONAL, INC., 2103 River FallsDrive, Kingwood, Tex. 77339, Phone: (281) 359-8520, Mr. Robert P.Radtke) bonding technology can be applied to combine materials andsystems. TII provides bonding technologies to join metals and ceramicsthat exhibit a large mismatch in the coefficient of thermal expansion.Brazing, dissimilar materials, initially silicon carbide to titaniumalloy Ti-6Al-4V, achieve the minimum attachment shear strength of 2× (76MPa, 11,000 psi), that of epoxy glues. TII recently developed novelmicrowave and combustion synthesis methods for brazing polycrystallinediamond and tungsten carbide for commercial abrasive applications.

In FIG. 3, the FuelCell Energy, Inc. Company fuel cell can be applied inthis invention. FuelCell Energy manufactures an SOFC that specifies apressure increase to several atmospheres to provide the fuel. If an SOFCis pressurized, an increased voltage results, leading to improvedperformance. For example, operation at 3 atmospheres increases the poweroutput by ˜10%. However, this improved performance alone may not justifythe expenses of pressurization, which require a compressor or hybridsource. During normal operation, air enters the compressor and iscompressed to ˜3 atmospheres. This compressed air passes through therecuperator, where it is preheated and then enters the SOFC. Pressurizedfuel from the fuel pump also enters the SOFC and the electrochemicalreactions take place along the cells.

Storing and releasing ammonia safely is important to this invention'ssuccess. Requirements: an ammonia storage tank filled with closed-cellfoam monolith and a tank capacity of 500 g (1.5 kWhe), an overall volumeof 1.2 liters, and a total mass of less than 950 g (including 500 gammonia). The maximum ammonia release rate will be low enough tominimize safety concerns yet high enough to supply the ammonia based insitu. One commercial source of such a tank is MESOSYSTEMS TECHNOLOGY,INC. 415 N Quay St., Bldg. A, Suite 5, Kennewick, Wash. 99336.Phone:(509) 222-2002.

ROCKY RESEARCH, 1598 Foothill Dr., P.O. Box 61800, Boulder City, Nev.89006, phone (702) 293-0851 provides ammonia storage in complexcompounds for a safe and compact hydrogen source. Complex compoundsabsorb ammonia in extremely high storage density. They can release thefull ammonia charge at constant pressure and are available withdifferent degrees of vapor pressure suppression for releasing ammonia atvariable rates to the hydrocarbon formation in situ. This is veryscalable method of delivering large quantities of ammonia or other gasesin an adsorption bed.

FIG. 15 illustrates the electrochemical synthesis of hydrogen peroxideon anthraquinone-modified electrode. The reduction of O₂ onquinone-modified electrodes proceeds according to theelectrochemical-chemical (EC) mechanism:

where Q is the attached quinone species. Reaction (II) is therate-determining step. The one-electron reduction of quinones yields theradical anion (Q^(.−)) which reacts with molecular oxygen in thefollowing chemical step to produce the superoxide radical anion (O₂^(.−)). The further reduction of O₂ ^(.−) and its catalyticdisproportionation are fast and both processes lead to the formation ofhydrogen peroxide. This can be varied to match formation.

Preparation of chemicals and energy using electrochemical principleswill be provided in situ. Kinetics of oxygen reduction on nanostructurednoble metal catalysts and on chemically modified electrodes will providea high density system for in situ. Nanostructured material is any solidmaterial that has a nanometer (1 nm=10⁻⁹ m) dimension. Nanoparticles ofplatinum and other noble metals are used in the preparation ofelectrodes for fuel cells. The preparation of noble metal catalysts in ahighly dispersive form on carbon supports enables to effectively utilizethese costly metals in practical devices. A fundamental question is howthe electrocatalytic properties of dispersed noble metals depend on theparticle size (this is called the “particle size effect”).

Major part of the research carried out in the frame of this project isaimed at systematically investigating the effect of particle size on thekinetics of O₂ reduction in acid solutions (HClO₄, H₂SO₄). Noble metalnanoparticles will be prepared on flat carbon substrates which can beconsidered as a model system for practical electrodes used in the fuelcells. The main advantages of the model system are as follows:nanoparticles on flat substrates are entirely accessible to O₂ moleculesfrom solution bulk and the surface characterisation of the modelcatalysts is easily feasible. The quinones are attached to the surfaceof carbon substrates by chemical modification. For this purpose, thediazonium salt reduction method and the anodic oxidation of carboxylatescould be used. There is a strong practical interest in the study ofelectrocatalytic properties of surface-bound quinones, because thesecatalyse the 2-electron reduction of O₂ to hydrogen peroxide:O₂+2H⁺+2e ⁻→H₂O₂

The quinone-modified carbon electrodes are potential candidates for theelectrochemical synthesis of hydrogen peroxide. The general scheme forperoxide generation is given by Professor David J. Schiffrin, Centre forNanoscale Science, Chemistry Department, University of Liverpool,Liverpool L69 7ZD, United Kingdom and available from industrial partnerJohnson Matthey.

FIG. 16 illustrates a simple ammonia SCF system. A bore hole 158 isdrilled through an overburden 154 and into a hydrocarbon-bearingformation 156. A casing 155 is cemented in a hydrocarbon-bearingformation 156 bore hole 158, sealing the outside. Inner casing seals 159hold the gas tube 152 in fluid communication with the perforations 160.Reactant (e.g. anhydrous ammonia, nitrous oxide, or hydrogen peroxide)are compressed in a tank 150 which is released through a regulator 151and gas tube 152 into the formation to produce SCF events 161. 162 is afuel cell in FIG. 15, which provides the electrochemical synthesis ofhydrogen peroxide on anthraquinone-modified electrodes. Fuel cell 162provides a safe transportation of water, or hydrogen and oxygen, intothe fuel cell in situ providing a safe down hole process away fromworkers. Ammonia, nitrous oxide, and all other reactants can be providedin situ, by providing fuel cells or catalytic systems in situ as closeto the safe delivery hydrocarbon formation as possible. Tubingtemperature capability, casing strength, formation depth, moisture, andformation type will determine how close to hydrocarbon-bearing formationthe safe chemicals can be converted into reactants for infusion into thehydrocarbon-bearing formation. In FIGS. 5-11 in situ heat exchangerillustrates tubes 50 with port 51, 52, 53, in fluid registration with51′, 52′, 53′, and 51″, 52″, 53″. Each of the six tubes 50 can have adifferent fuel cell type, catalysis material, or reformer to processfluids into reactants down hole, or to refine hydrocarbons recoveredfrom hydrocarbon-bearing formations. Dissolved crude fossil fuel enableson-site fuel cell refining.

In FIG. 17 graphite monolithic bricks 174 (172) are produced withfibrous ends 173 and 175 spaced for fluid penetration and high surfacearea contact with fluids, which provide a coated electrode to convertchemical energy into electrical energy and a path to conduct (or store)electrical or thermal energy through the axis 177. The electrical andthermal conductivity in the axial (planar) 177 direction issignificantly higher than for conventional graphite. The restitivity inthis plane is about 55 mW per meter. The electrical and thermalconductivity in the longitudinal direction 176 is significantly lowerthan for conventional graphite. In this plane, restitivity is about 2.5mW per meter. EnergyBrush is a graphite refractory brick with enhancedthermal insulation when the hot fibrous edges are protected from a heattransfer event. Heat storage occurs when heat in fluid is absorbed in170 the graphite brick's fibrous edges and cannot escape from a face.Colder fluid contacting the hot fibrous edges removes the heat 171 fromthe brick. Energy is introduced 170 or removed 171 at high surface area“fiber” ends 173 and 175 of graphite brick (monolith). High surface area“fiber” ends 173 and 175 converts SCFs to electrolytes when electrode iscooled in contact with SCFs.

SCFs dissolve/evaporate hydrocarbons to a more refined level in the 1stphase of recovery, making on-site fuel cell assisted refining economicand replacing future large refineries without the objection of “not inmy backyard”:

Fuel cell elements—fuel, product, proton exchange membrane (PEM),cathode, and anode are operated within SCFs in situ or on site toincrease electrical and chemical reaction efficiencies magnitudes morethan prior art, operating below the critical point of gas, liquids, andsolids.

Portable mass spectrometers can rapidly and accurately measure crude oilto see if SCF events occurred and royalty fees are due: A uniquechemical “ID” is present because only SCFs can dissolve HBF solids insitu. Prior SCF art does not teach that “open” porous geologicformations can provide the environment for a SCF event to movehydrocarbons out of the HBFs. SCF oil and gas recovery focuses onbreaking down the hydrocarbons in HBFs to produce motive forces withhydrocarbon reactants or inorganic compounds. Gas molecules can travelonly short distances in straight lines before high-speed deflection in anew direction by collision with other gas molecules. “Spontaneous” SCFcells form within natural composites of open rocks, clay, andhydrocarbon liquids or solids when gas molecules traveling in a“reaction zone” build pressure and temperature rapidly enough to moveabove the critical point: Solids dissolve and liquids evaporate at greatefficiency even though SCF cell phases last only a few seconds permicro-burst of energy. SCFs form one solution from many natural in situHBF gas/liquid species and penetrate deep inside all HBFs in the sameway, as deep as one scGAS, with nearly 100% penetration. SCFs provide amore economic oil/gas recovery technology in the 1st phase: SCFsdissolve/evaporate hydrocarbons in the 1st phase. Low-energy infusion ofhydrocarbon-reactant compounds into hydrocarbon-bearing formationsviolently react (micro-bursts of energy) with hydrocarbons, forming“spontaneous” micro-cells of SCFs that dissolve and evaporatehydrocarbons, producing a motive force at great distances from theborehole. Economic benefits of dissolving hydrocarbons are in the 1stphase of oil/gas recovery because of SCFs' unique ability to penetratenear 100% of any HBF, dissolve materials into their components, diffusesolids, and then evaporate liquids into an “internal” global motiveforce.

Supercritical fluid penetration into hydrocarbon-bearing formations insitu increases hydrocarbon recovery economics in the first phase. Thisinvention teaches direct injection of supercritical fluids intohydrocarbon-bearing formations to remove hydrocarbons from the infusionregion of near the down hole casing and then injectioning reactants thatwill travel great distances for spontaneous reactions withhydrocarbon-bearing formation to form SCFs. Economic benefits ofpenetrating HBFs with SCFs: Hydrocarbon-reactant infusion has a lowenergy cost. Motive forces are produced in HBFs at great distances. Near100% penetration of any natural geologic HBF: Coal, tar-sands, heavyoil, shale, HBFs, and sub-soil remediation A company's fossil fuelreserves can be diversified by SCF economics. Carbon dioxide (CO2)phases into scCO2 (SCF) after it rises in temperature and pressure aboveits thermodynamic critical point.

Liquids evaporate and solids dissolve at great efficiency even thoughSCF cell phases last only a few seconds per micro-burst of energy deepwithin HBFs. The present invention has been described in relation to apreferred embodiment and several alternative preferred embodiments. Oneof ordinary skill, after reading the foregoing specification, may beable to affect various other changes, alterations, and substitutions orequivalents thereof without departing from the concepts disclosed. It istherefore intended that the scope of the Letters Patent granted hereonbe limited only by the definitions contained in the appended claims andequivalents thereof.

1. A method for the in-situ recovery of hydrocarbons fromhydrocarbon-bearing formations comprising: forming a bore hole sealassembly having an elongated substantially cylindrical outer housing,providing said elongated bore hole seal assembly with an interiorcontaining a port to an upwardly extending intake air supply line andincluding in said upwardly extending intake air supply line a minorreactive gas intake regulator and valve, drilling two bore holes into asubterranean hydrocarbon-bearing formation, lowering said elongated borehole seal assembly into one of two said bore holes to a positionsurrounded by the hydrocarbon-bearing formation with said first andsecond bore holes having been drilled to define a diameter relative tosaid elongated bore hole seal assembly housing, insuring a close fitthere between while providing a gas space between, providing a pluralityof seal members within said bore hole around said elongated bore holeseal assembly restricting gas leaks, whereby supplying a major inert gasto said supply line from gas supply means disposed above ground,supplying a minor reactive gas that is reactive to hydrocarbon to saidregulator valving in major inert gas air line from gas supply meansdisposed above ground, regulating said major inert gas supply means andsaid minor reactive gas supply means to progressively and radiallyinfuse gas into surrounding undisturbed hydrocarbon-bearing formation,monitoring the hydrocarbon-bearing formations and manipulating saidregulation of said gas supply means to maintain supercritical fluid(SCF) gas cell formation in hydrocarbon-bearing formation, insuring,during said regulating of said major inert gas supply means and saidminor reactive gas supply means, that microbursts of reactive gas formSCF from the major inert gas reacting with hydrocarbons, insuring,during said monitoring of the temperature and pressure of thehydrocarbon-bearing formation, that a pressure at over 1 to 7atmospheres is maintained, whereby, collecting the hydrocarbon generatedfrom said first bore hole through said adjacent bore hole near the samehydrocarbon-bearing formation.
 2. The method according to claim 1wherein, said seals are horizontally located to separate gases.
 3. Themethod according to claim 2 wherein, said working fluid is nitrogendiamers.
 4. The method according to claim 2 wherein, said working fluidis nitrogen compounds.
 5. The method according to claim 4 wherein, saidworking fluid is reactive with hydrocarbons.
 6. The method according toclaim 5 wherein, said working fluid violently reacts with hydrocarbonsin microbursts to instantly compress surrounding inert gas into SCF. 7.The method according to claim 6 wherein, said SCF saturates hydrocarbonsin hydrocarbon-bearing formations followed by an immediate bubbling,energy release, and migration of hydrocarbons out of hydrocarbon-bearingformations.
 8. The method according to claim 2 wherein, said workingfluid is nitrogen compound anhydrous ammonia.
 9. The method according toclaim 2 wherein, said working fluid is nitrogen compound nitrates. 10.The method according to claim 2 wherein, said working fluid is nitrogencompound nitrites.
 11. The method according to claim 2 wherein, saidworking fluid is nitrogen compound azides.
 12. A method for the in-siturecovery of hydrocarbons from hydrocarbon-bearing formations comprising:forming a heater assembly having an elongated substantially cylindricalouter housing, providing said elongated heater assembly with an interiorcontaining a fuel cell therein joined to an upwardly extending intakeair supply line and including in said interior an upwardly extendingexhaust gas line disposed adjacent an upwardly extending combustion airline, drilling a bore hole into a subterranean hydrocarbon-bearingformation, lowering said fuel cell assembly into said bore hole to aposition surrounded by the hydrocarbon-bearing formation, with said borehole having been drilled to define a diameter relative to said fuel cellassembly housing insuring a close fit there between while providing agas space between, providing a plurality of seal members within aid borehole above said heater assembly, whereby supplying fuel gas to said fuelgas supply line from fuel gas supply means disposed above ground,supplying air to said air line from air supply means disposed aboveground, regulating said gas supply means and said combustion air supplymeans to operate said fuel cells in heater assembly and said heaterassembly outer housing and thence, through convection and radiation, toprogressively and radially heat the surrounding undisturbedhydrocarbon-bearing formation, monitoring the temperature of the heatedhydrocarbon-bearing formations and manipulating said regulating of saidsupply means to maintain the temperature of the heatedhydrocarbon-bearing formations at approximately 1200° F. to 1800° F.,insuring, during said regulating of said gas supply means and said airsupply means, that a temperature of over 150° C. is maintained,insuring, during said monitoring of the temperature of the heatedhydrocarbon-bearing bed formation, that a temperature in the range of150° C. to 1371° C. and gas pressure at 3 to 7 atmospheres ismaintained, whereby, collecting the hydrocarbon generated gases fromsaid bore hole through said fuel cell line and natural gas within saidbore hole is precluded from exiting said bore hole other than throughsaid fuel cells.